EP2328862B1 - Diamide enthaltendes produkt, verfahren zu dessen herstellung und anwendungen davon - Google Patents

Diamide enthaltendes produkt, verfahren zu dessen herstellung und anwendungen davon Download PDF

Info

Publication number
EP2328862B1
EP2328862B1 EP09783247.1A EP09783247A EP2328862B1 EP 2328862 B1 EP2328862 B1 EP 2328862B1 EP 09783247 A EP09783247 A EP 09783247A EP 2328862 B1 EP2328862 B1 EP 2328862B1
Authority
EP
European Patent Office
Prior art keywords
product
compound
noc
formula
formulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP09783247.1A
Other languages
English (en)
French (fr)
Other versions
EP2328862A1 (de
Inventor
Massimo Guglieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2328862A1 publication Critical patent/EP2328862A1/de
Application granted granted Critical
Publication of EP2328862B1 publication Critical patent/EP2328862B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5095—Mixtures including solvents containing other heteroatoms than oxygen, e.g. nitriles, amides, nitroalkanes, siloxanes or thioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides

Definitions

  • the present invention relates to novel products comprising diamide compounds, uses of the products and at least one method of preparation. These products can in particular be used as solvents, for example in phytosanitary formulations.
  • solvents are used for the formulation of phytosanitary assets, especially in the form of emulsifiable concentrates (Emulsifiable Concentrate "EC") intended to be diluted in water by the farmer, before application to a field.
  • EC emulsifiable Concentrate
  • the industry is looking for new products to vary or optimize products and processes in which solvents, including polar solvents, are to be used.
  • solvents including polar solvents
  • the industry needs low cost compounds with interesting properties of use.
  • the industry also needs compounds with a toxicological and / or ecological profile perceived as favorable, in particular low volatility (low VOC), good biodegradability, low toxicity and / or low hazard.
  • dialkylamides The use as solvents of dialkylamides is known. It is a product of formula R-CONMe 2 or R is a hydrocarbon group such as an alkyl, typically C 6 -C 30 . Such products are in particular marketed under the name Genagen® by the company Clariant. These solvents find applications particularly in the phytosanitary field.
  • the diesters of dicarboxylic acids are also known as solvents, in particular the diesters obtained by esterification of a mixture of adipic acid, glutaric acid and succinic acid.
  • solvents such products are marketed under the names Rhodiasolv® RPDE and Rhodiasovl® DIB by Rhodia.
  • the document US 4588833 describes the preparation of substituted succinic acid amides.
  • This document describes in particular the preparation of compounds of XOC-CH 2 -CHR 6 -CONEt 2 type where R 6 is a methyl or an ethyl.
  • the products are prepared by bringing CO, an alcohol or an amine HX, and crotonic acid dialkylamide or pent-3-enoic acid diethylamide.
  • the document teaches the use of the compounds as anti-oxidants, as stabilizers for plastics, or as organic synthesis intermediates.
  • mixtures or combinations can be liquid while the components are individually solid.
  • the invention also relates to a process for preparing the product of the invention.
  • the invention also relates to the use of the product of the invention in formulations.
  • the invention also relates to a process for preparing the formulations by adding the product of the invention.
  • the invention also relates to formulations comprising the product of the invention.
  • the formulations may in particular be phytosanitary formulations.
  • the invention also relates to the use of the product of the invention as solvent, plasticizer, or coalescing agent.
  • solvent is understood in a broad sense, covering in particular the co-solvent functions, crystallization inhibitor, stripper.
  • solvent can in particular designate a liquid product at the temperature of use, preferably having a melting point of less than or equal to 20 ° C., preferably at 5 ° C., preferably at 0 ° C., which can contribute to making liquid a liquid. solid material, or to prevent or retard the solidification or crystallization of material in a liquid medium.
  • a compound corresponding to a chemical formula means any compound responding to said. It is mentioned that the term "compound” also covers mixtures of several molecules corresponding to the same formula. It can therefore be a molecule of said formula, or a mixture of several molecules corresponding to said formula.
  • a compound of formula (Ia) may be a molecule of formula (Ia) with defined groups R 2 , R 3 , R 4 and R 5 , or a mixture of several molecules corresponding to formula (Ia), said molecules having between them differences as regards the groups R 2 , R 3 , R 4 and R 5
  • composition of matter means a composition, more or less complex, comprising several chemical compounds. It can typically be an unpurified or modestly purified reaction product.
  • the compound of the invention may in particular be isolated and / or marketed and / or used in the form of a composition of matter comprising it.
  • the product of the invention is a composition of matter.
  • all the compounds of formulas (Ia), (Ib) and (Ic) may represent at least 10% by weight. Preferably, all of these compounds constitute the main product of the composition of matter.
  • main product in the present application, the product whose content is the highest, even if its content is less than 50% by weight (for example in a mixture of 40% of A, 30% of B, and 30% of C, product A is the product main).
  • all the compounds of formulas (Ia), (Ib) and (Ic) represent at least 50% by weight of the composition of matter, for example from 70 to 95% by weight, and even 75 to 90% by weight.
  • the product may comprise at least two of the compounds of formulas (Ia), (Ib) and (Ic). It preferably comprises the three compounds.
  • a a , A b , and A c are linear divalent alkyl groups, each comprising a different number of carbon atoms.
  • Groups A a, A b and A c correspond to the diacids of formula HOOC-A-COOH, HOOC-A-COOH b, and c HOOC-A-COOH.
  • the mixture of the compounds in these proportions can correspond (in amide version) to a mixture of Adipic, Glutaric and Succinic acids ( "AGS") available in large quantities as a by-product of the adipic acid preparation, a monomer used in the manufacture of polyamide or polyurethane.
  • ASS Adipic, Glutaric and Succinic acids
  • the mixture of diacids or diesters obtained from the mixture of diacids can be a raw material of particular interest from an economic, industrial and environmental point of view because a by-product is used and the use of resources is optimized.
  • the groups R 2 , R 3 , R 4 and R 5 which are identical or different, are groups chosen from hydrocarbon groups comprising an average number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, optionally substituted, R 2 and R 3 on the one hand and R 4 and R 5 on the other hand may optionally together form a ring, optionally substituted and / or optionally comprising a heteroatom.
  • the ring typically comprises the nitrogen atom to which R 2 and R 3 or R 4 and R 5 are linked.
  • the cycle may comprise an additional heteroatom.
  • the substituent may be a hydroxy group.
  • the pairs R 2 and R 3 on the one hand and R 4 and R 5 on the other hand are identical pairs.
  • R 2 and R 3 are identical.
  • R 4 and R 5 are identical.
  • R 2 , R 3 , R 4 and R 5 are identical
  • the groups R 2 , R 3 , R 4 and R 5 which are identical or different, are chosen from methyl, ethyl, propyl (n-propyl), isopropyl, n-butyl, isobutyl and n-pentyl groups. , amyl, isoamyl, hexyl, cyclohexyl, hydroxyethyl.
  • the groups R 2 and R 3 may also be such that together they form with the nitrogen atom a morpholine, piperazine or piperidine group.
  • the product of the invention may comprise at least 10% by weight, preferably at least 50% by weight, preferably at least 75%, for example at least 95%, of the compounds of formulas (Ia), ( Ib) and (Ic).
  • the product may be an ingredient or aid to processes intended to be combined with other ingredients or to be carried out in the presence of other chemical compounds.
  • the product may be a composition or formulation comprising other ingredients.
  • compounds (Ia), (Ib) and (Ic) can be introduced separately into the product. However, it is preferred to introduce them as a mixture or premix. According to a preferred embodiment the product is derived from a mixture wherein the compounds (Ia), (Ib) and (Ic) are present.
  • the product may in particular be a product for amidification or trans-amidification.
  • the product of the invention advantageously has a melting point less than or equal to 35 ° C, preferably less than or equal to 25 ° C, preferably less than or equal to 10 ° C, preferably less than or equal to 0 ° C.
  • the product of the invention can be prepared by any suitable method. It is particularly preferred to carry out amidification or trans-amidification reactions on diacids or similar diesters, preferably in analogous mixtures. Such reactions are known to those skilled in the art.
  • a suitable method for preparing a product of the invention may be a process comprising a step of amidification or trans-amidification with a compound of formula R 2 R 3 NH and / or HNR 4 R 5 of a mixture at least two compounds, preferably all three, chosen from the following compounds of formulas (a), (I'b) and (I'c): R 8 OOC-A a -COO R 8 (I'a) R 8 OOC-A b -COO R 8 (I'b) R 8 OOC-A c -COO R 8 (I'c) where R 8 is a hydrogen atom or a C 1 -C 6 alkyl, preferably a methyl.
  • the compounds of formulas (a), (I'b), and (I'c) are considered analogous diacids or diesters respectively diamide compounds.
  • the amidification or trans-amidating reaction can be carried out continuously, semi-continuously, or batchwise.
  • conversion rate of the reaction conversion rate of the acid or diesters
  • conversion rate of the acid or diesters conversion rate of the acid or diesters
  • conversion rate of the acid or diesters conversion rate of the acid or diesters
  • the alcohols formed during a trans-amidification reaction can be removed by stripping. It is noted that it is possible to use a very large excess of amine, an amine salt or any other means known to those skilled in the art, for example described in the book " March's Advanced Organic Chemistry "by Michael B. Smith and Jerry March, 5th Edition, John Wiley & Sons, pages 506-511 .
  • the reaction may be followed by filtration and / or purification steps, for example by distillation.
  • amidification or trans-amidating reaction can pass through activated intermediates such as the acid chlorides obtained, for example, from the compounds of formulas (a), (I'b), (I c) by reaction with thionyl chloride.
  • activated intermediates such as the acid chlorides obtained, for example, from the compounds of formulas (a), (I'b), (I c) by reaction with thionyl chloride.
  • the separation of the hydrochloric acid by-product during this type of amidification reaction, the reaction medium by any suitable means (salt formation, distillation), is a motor for moving the reaction equilibrium towards the formation of amide sought.
  • the diacids or diesters in the form of mixtures may especially be mixtures of diacids derived from the manufacture of adipic acid (so-called AGS mixture) or diesters obtained from these diacid mixtures. Mixtures of diesters are in particular marketed under the name Rhodiasolv® RPDE.
  • the product of the invention may especially be used as a solvent, co-solvent and / or crystallization inhibitor, as a plasticizer or as a coalescing agent.
  • co-solvent is meant that other solvents may be associated with it.
  • the use as a solvent or co-solvent includes the use to dissolve a compound in a formulation, in a reaction medium, the use to solubilize totally or partially a product to be removed (degreasing, stripping), and / or or to facilitate take-off of material films.
  • the product of the invention may especially be used, for the functions indicated above or for others, in a phytosanitary formulation, in a cleaning formulation, in a pickling formulation, in a degreasing formulation, in a formulation lubricants or textiles, in a coating formulation, for example in a paint formulation, in a pigment formulation or ink, in a plastic formulation.
  • the product may for example be used as a coalescing agent in an aqueous paint formulation.
  • the product can in particular be used as a resin solvent, for example in the cable coating industry or in the electronics industry, especially as a solvent for PVDF.
  • the product can be used as a cleaning and / or pickling solvent in the electronics industry. It can especially be used in lithium batteries. It can especially be used on photoresistant resins, polymers, waxes, fats, oils.
  • the product can in particular be used for cleaning inks, for example during the production of inks or when printing ink is used.
  • the product can especially be used for cleaning sieves or other tools used in manufacturing processes and / or recycling paper.
  • the product can in particular be used for the cleaning of bitumen or tar sand, for example on coated substrates, on the tools used to apply these materials, on contaminated clothing, on soiled vehicles.
  • the product can especially be used for cleaning flying machines such as airplanes, helicopters, space shuttles.
  • the product may especially be used as a degreasing agent on metal surfaces, for example surfaces of tools, manufactured articles, sheets, molds, in particular steel or aluminum or alloys of these metals.
  • the product can be used as a cleaning solvent on hard surfaces or textile surfaces.
  • the product can in particular be used as a solvent for stripping paint or resins, on tool surfaces, for example foundry molds, on surfaces of industrial sites (floors, partitions, etc.).
  • the paint stripping formulations may in particular be aqueous-based formulations (the compound being in admixture with water) or solvent-based (the compound then being the solvent or a compound mixed with water).
  • the product can in particular be used as a plasticizer in thermoplastic polymer formulations.
  • the cleaning and / or degreasing formulations may in particular be formulations for household care, operated in homes or in public areas (hotels, offices, factories, etc.). These can be formulations for cleaning hard surfaces such as floors, furniture and equipment surfaces in kitchens and bathrooms, and dishes. These formulations can also be used in the industrial sphere to degrease manufactured products and / or cleaned. Such formulations may in particular be used to clean and / or strip products, tools, molds, clothes or other.
  • the product of the invention may especially be used in phytosanitary formulations comprising a solid active product. More details are given below, where the word “solvent” may refer to the product of the invention.
  • Diacid diesters (“DiBasic Esters”) are also mentioned, in particular those marketed by Rhodia under the trade names Rhodiasolv RPDE and Rhodiasolv DIB. Also mentioned are hydrocarbon cuts, cyclic amides such as NMP, lactones. The bis (dialkylamides) which are the subject of the document WO 2008 // 074837 .
  • the phytosanitary formulation is generally a concentrated phytosanitary formulation comprising an active compound.
  • the phytosanitary formulations must allow easy weight dilution by the farmer, in order to obtain a product in which the phytosanitary product is correctly dispersed, for example in the form of a solution, emulsion, suspension, or suspension. emulsion.
  • the phytosanitary formulations thus allow the transport of a phytosanitary product in relatively concentrated form, easy packaging and / or easy handling for the end user.
  • Different types of phytosanitary formulations can be used depending on the different plant protection products.
  • Emulsifiable concentrates Emulsifiable Concentrates “EC”
  • EW concentrated emulsions
  • ME microemulsions
  • WP wettable powders
  • WDG Water Dispersible Granules
  • the formulations that can be used depend on the physical form of the phytosanitary product (for example solid or liquid), and its physico-chemical properties in the presence of other compounds such as water or solvents.
  • the phytosanitary product may be in various physical forms: solution, dispersion of solid particles, dispersion of droplets of the product, droplets of solvent in which the product is dissolved ...
  • the formulations Phytosanitary products generally include compounds that make it possible to obtain these physical forms. It may for example be surfactants, solvents, mineral carriers, and / or dispersants. Often these compounds do not have an active character, but a character of intermediary for formulation aid.
  • the phytosanitary formulations may in particular be in liquid form, or in solid form.
  • the phytosanitary formulation thus comprises a solution of the product in the solvent.
  • the formulation may be in solid form, for example in the form of a wettable powder (WP) in which the solution soaks an inorganic support, for example kaolin and / or silica.
  • WP wettable powder
  • the formulation may alternatively be in liquid form, for example in the form of an emulsifiable concentrate (EC) having a single clear liquid phase comprising the solvent and the product in solution, capable of forming an emulsion by adding water, without stirring or with a weak agitation.
  • EC emulsifiable concentrate
  • EW concentrated emulsion
  • ME clear microemulsion
  • tebuconazole is a particularly effective and widely used fungicide for soybean cultivation in particular.
  • Crystals can have negative effects, including clogging the filters of the devices used to spread the diluted composition, clog the spray devices, decrease the overall activity of the formulation, create unnecessary problems of waste streams to remove the crystals, and / or cause a bad distribution of the active product on the agricultural field.
  • Active plant protection products especially non-water soluble and solid products are known to those skilled in the art.
  • the active plant protection product may in particular be a herbicide, an insecticide, an acaricide, a fungicide, or a rodent killing agent ("rodenticide" in English) for example a rat poison.
  • suitable active ingredients mention may be made, inter alia, of Amtretryne, Diuron, Linuron, Chlortoluron, Isoproturon, Nicosulfuron, Metamitron, Diazinon, Aclonifen and Atrazine.
  • Chlorothalonil Bromoxynil, Bromoxynil heptanoate, Bromoxynil octanoate, Mancozeb, Maneb, Zineb, Phenmedipham, Propanyl, phenoxyphenoxy series, heteroaryloxyphenoxy series, CMPP, MCPA, 2,4 -D, Simazine, the active products of the imidazolinones series, the organophosphorus family, with in particular Azinphos-ethyl, Azinphos-methyl, Alachlor, Chlorpyriphos, Diclofop-methyl, Fenoxaprop-p Methyl Chlorine, Methoxychlor, Cypermethrin, Fenoxycarb, Cymoxanil, Chlorothalonyl, neonicotinoid insecticides, triazole fungicide family such as azaconazole, bromuconazole, cyproconazole, difenoconazole, dini
  • active plant protection products may be used: Alachlor, Chlorpyrifos, alpha-cypermethrin, Phenmedipham, Propanil, Pendimethalin, Triadimenol, Trifluralin, Oxyfluorfen, Dimethoate, Imidacloprid, Proxopur, Benomyl, Deltamethrin, Fenvalerate, Abamectin, Amicarbazone, Bifenthrin, Carbosulfan, Cyfluthrin, Difenconazole, Ethofenprox, Fenoxaprop-ethyl, Fipronil, Fenvalerate, Fluazifop-p-butyl, Flufenouron, Hexazinone, Lambda-cyalothrin, Methomyl, Permethrin, Prochloraz, Propiconazole, Tebuconazole
  • the phytosanitary formulation may comprise an emulsifying agent, typically and preferably a surfactant.
  • the emulsifying agents are agents intended to facilitate the emulsification or dispersion after placing the formulation in contact with water, and / or to stabilize (in time and / or in temperature) the emulsion or the dispersion. for example by avoiding sedimentation.
  • Surfactants are known compounds, which have a generally relatively low molar mass, for example less than 1000 g / mol.
  • the surfactant can be an anionic surfactant in salified or acidic form, preferably polyalkoxylated nonionic, cationic, amphoteric (term also including zwitterionic surfactants). It may be a mixture or combination of these surfactants.
  • the anionic surfactants can be in acid form (they are potentially anionic), or in partially or totally salified form, with a counterion.
  • the counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of formula N (R) 4 + in which R, identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted with an oxygen atom.
  • the formulation advantageously comprises at least 4%, preferably at least 5%, preferably at least 8%, by weight of dry matter, of at least one surfactant c).
  • the solvent may be combined with an aromatic and / or nonaromatic surfactant.
  • the phytosanitary formulation preferably does not include significant amounts of water.
  • the water content is less than 50% by weight, preferably less than 25% by weight. It will generally be less than 10% by weight.
  • the formulation is preferably a liquid formulation, for example in the form of an emulsifiable concentrate (EC), a concentrated emulsion (EW) or a micoremulsion (ME).
  • EC emulsifiable concentrate
  • EW concentrated emulsion
  • ME micoremulsion
  • it preferably comprises less than 500 g / l of water, more preferably less than 250 g / l. It will generally be less than 100 g / L.
  • solid formulations for example formulations in which a liquid comprising the phytosanitary product solubilized in the solvent, is supported by a mineral and / or dispersed in a solid matrix.
  • the formulation may of course include other ingredients (or "other additives") than the active plant protection product, the solvent (s), the optional emulsifying agent (s) and the optional water. It may especially comprise viscosity modifiers, defoamers, especially silicone antifoams, anti-rebound agents, anti-leaching agents, inert fillers, in particular mineral fillers, anti-freeze agents, etc.
  • the concentrated phytosanitary formulation is intended to be spread over a cultivated field or to be cultivated, for example a soybean field, most often after dilution in water, to obtain a diluted composition.
  • Dilution is generally carried out by the farmer, directly in a tank ("tank-mix"), for example in the tank of a device for spreading the composition. It is not excluded that the operator adds other phytosanitary products, for example fungicides, herbicides, pesticides, insecticides, fertilizers.
  • the formulation can be used to prepare a composition diluted in the water of the active plant protection product, by mixing at least one part by weight of concentrated formulation with at least 10 parts of water, preferably less than 1000 parts. Dilution rates and amounts to be applied in the field usually depend on the crop product and the desired dose to treat the field; this can be determined by the farmer.
  • Diamide mixtures are prepared from diacid mixtures.
  • the mixture of diacids and thionyl chloride are mixed at room temperature.
  • the reaction mixture can be refluxed to complete the reaction.
  • the volatile species are removed by distillation under reduced pressure to obtain the crude product which is typically used as such without further purification.
  • Procedure B Formation of diamide (as a mixture) by reaction with a dialkylamine
  • Toluene and triethylamine are charged and cooled to -10 ° C.
  • the dialkylamine is then charged in liquid form.
  • the acid dichloride (as a mixture), diluted in toluene, is then slowly added while maintaining the temperature below + 10 ° C.
  • the mixture is then stirred for two hours at room temperature.
  • the salts formed during the reaction are then filtered and washed with ethyl acetate.
  • the filtrate thus obtained is evaporated on a rotary evaporator to obtain the crude reaction.
  • the final product is finally obtained after distillation under reduced pressure.
  • Example 1.1 Preparation of a product comprising a mixture of the following compounds:
  • the product is observed at different temperatures. It is found to be liquid at temperatures of 35 ° C, 30 ° C, 25 ° C, 20 ° C, 10 ° C. It is also found that it is free of crystals at these temperatures.
  • Dialkyl diamide (as a mixture) is obtained by Procedure B.
  • Gross product 1068 g (brown liquid)
  • Final product 700 g (slightly yellow liquid)
  • the product obtained is analyzed by gas chromatography.
  • the analysis indicates (in peak area): And 2 NOC-CH 2 -CH 2 -CONEt 2 13.09% And 2 NOC-CH 2 -CH 2 -CH 2 -CONEt 2 70.60% And 2 NOC-CH 2 -CH 2 - CH 2 -CH 2 -CONE 2 12.71%
  • the product is observed at different temperatures. It is found to be liquid at temperatures of 35 ° C, 30 ° C, 25 ° C, 20 ° C, 10 ° C, 0 ° C, -10 ° C. It is also found that it is free of crystals at these temperatures.
  • Examples 2 are comparative examples in which the product Rhodiasolv® ADMA10, Rhodia (Asia-Pacific zone) is used as solvent: Alkydimethylamide solvent.
  • the following EC formulation is prepared: Imidacloprid tech.98% 204 g / L Solvent of Example 1.1 856 g / L Soprophor® 769 / P (surfactant, Rhodia) 150 g / L
  • the properties of the formulation are evaluated after 14 days at 54 ° C: - pH (Cipoac MT 75 method): 3.0 - Emulsification (Cipac test, at 0.5% concentration at 30 ° C, after 2 hours AT D VS 0t 0 0

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (11)

  1. Erzeugnis umfassend mindestens zwei Diamid-Verbindungen ausgewählt aus den Diamid-Verbindungen der folgenden Formeln (Ia), (Ib) und (Ic):

            R2R3NOC-Aa-CONR4R5     (Ia)

            R2R3NOC-Ab-CONR4R5     (Ib)

            R2R3NOC-Ac-CONR4R5     (Ic)

    wobei:
    - R2, R3, R4 und R5, identisch oder verschieden, ausgewählt sind aus Methyl-, Ethyl-, Propyl- (n-Propyl-), Isopropyl-, n-Butyl-, Isobutyl-, n-Pentyl, Amyl-, Isoamyl-, Hexyl-, Cyclohexyl-, Hydroxyethyl-, Morpholin-, Piperazin- oder Piperidingruppen;
    - Aa die Gruppe der folgenden Formel -CH2-CH2- (Ethylen) ist,
    - Ab die Gruppe der folgenden Formel -CH2-CH2-CH2- (n-Propylen) ist, und
    - Ac die Gruppe der folgenden Formel -CH2-CH2-CH2-CH2- (n-Butylen) ist.
  2. Erzeugnis gemäß einem der vorangehenden Ansprüche, gekennzeichnet dadurch, dass es die drei Verbindungen der Formeln (Ia), (Ib) und (Ic) umfasst.
  3. Erzeugnis gemäß einem der vorangehenden Ansprüche, gekennzeichnet dadurch, dass es im Verhältnis zur absoluten Molzahl der Diamide der Formeln (Ia), (Ib) und (Ic):
    - von 1 bis 20 Mol-%, vorzugsweise von 5 bis 15 Mol-% an Diamid der Formel (Ic),
    - von 45 bis 75 Mol-%, vorzugsweise von 55 bis 65 Mol-% an Diamid der Formel (Ib) und
    - von 15 bis 45 Mol-%, vorzugsweise von 20 bis 33 Mol-% an Diamid der Formel (Ia)
    umfasst.
  4. Erzeugnis gemäß einem der vorangehenden Ansprüche, gekennzeichnet dadurch, dass:
    - die Verbindung der Formel (Ia) die Verbindung Me2NOC-CH2-CH2-CONMe2 ist,
    - die Verbindung der Formel (Ib) die Verbindung Me2NOC-CH2-CH2-CH2-CONMe2 ist, und
    - die Verbindung der Formel (Ic) die Verbindung Me2NOC-CH2-CH2-CH2-CH2-CONMe2 ist.
  5. Erzeugnis gemäß einem der Ansprüche 1 bis 3, gekennzeichnet dadurch, dass:
    - die Verbindung der Formel (Ia) die Verbindung Et2NOC-CH2-CH2-CONEt2 ist,
    - die Verbindung der Formel (Ib) die Verbindung Et2NOC-CH2-CH2-CH2-CONEt2 ist, und
    - die Verbindung der Formel (Ic) die Verbindung Et2NOC-CH2-CH2-CH2-CH2-CONEt2 ist.
  6. Erzeugnis gemäß einem der vorangehenden Ansprüche, gekennzeichnet dadurch, dass es mindestens 10 Gew.-%, vorzugsweise mindestens 50 Gew.-% an Verbindungen der Formeln (Ia), (Ib) und (Ic) umfasst.
  7. Erzeugnis gemäß Anspruch 6, gekennzeichnet dadurch, dass es ein Amidierungsprodukt oder ein trans-Amidierungsprodukt ist.
  8. Erzeugnis gemäß einem der vorangehenden Ansprüche, gekennzeichnet dadurch, dass es eine Schmelztemperatur von weniger als oder gleich 35 °C, vorzugsweise weniger als oder gleich 25 °C, vorzugsweise weniger als oder gleich 10 °C, vorzugsweise weniger als oder gleich 0 °C aufweist.
  9. Verfahren zur Herstellung eines Erzeugnisses gemäß einem der vorangehenden Ansprüche, umfassend einen Amidierungs- oder trans-Amidierungsschritt einer Verbindung der Formel R2R3NH und/oder HNR4R5 einer Mischung von mindestens zwei Verbindungen ausgewählt aus den Verbindungen der folgenden Formeln (I'a), (I'b) und (I'c):

            R8OOC-Aa-COO R8     (I'a)

            R8OOC-Ab-COO R8     (I'b)

            R8OOC-Ac-COO R8     (I'c)

    wobei R8 ein Wasserstoffatom oder ein C1-C6-Akyl ist, vorzugsweise ein Methyl.
  10. Verwendung eines Erzeugnisses, wie in einem der Ansprüche 1 bis 8 definiert, als Lösemittel, Weichmacher oder Koaleszenzmittel.
  11. Verwendung eines Erzeugnisses, wie in einem der Ansprüche 1 bis 8 definiert, in einer Pflanzenschutzmittelformulierung, in einer Reinigungsformulierung, in einer Beizformulierung, in einer Entfettungsformulierung, in einer Schmiermittelformulierung, in einer Beschichtungsformulierung, in einer Pigment- oder Tintenformulierung, oder in einer Kunststoffformulierung.
EP09783247.1A 2008-09-22 2009-09-21 Diamide enthaltendes produkt, verfahren zu dessen herstellung und anwendungen davon Active EP2328862B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0805188A FR2936129B1 (fr) 2008-09-22 2008-09-22 Produit comprenant des diamides, procede de preparation et utilisations
PCT/EP2009/062208 WO2010031867A1 (fr) 2008-09-22 2009-09-21 Produit comprenant des diamides, procede de preparation et utilisations

Publications (2)

Publication Number Publication Date
EP2328862A1 EP2328862A1 (de) 2011-06-08
EP2328862B1 true EP2328862B1 (de) 2015-10-21

Family

ID=40568776

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09783247.1A Active EP2328862B1 (de) 2008-09-22 2009-09-21 Diamide enthaltendes produkt, verfahren zu dessen herstellung und anwendungen davon

Country Status (6)

Country Link
US (1) US20120029092A1 (de)
EP (1) EP2328862B1 (de)
AR (1) AR075276A1 (de)
ES (1) ES2557597T3 (de)
FR (1) FR2936129B1 (de)
WO (1) WO2010031867A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2364591A1 (de) * 2010-03-09 2011-09-14 Cognis IP Management GmbH Biozidzusammensetzungen, die Dicarbonsäurealkylamide umfassen
US20200181065A1 (en) 2016-04-06 2020-06-11 Rhodia Operations N-alkyldiamide compounds and gels comprising the same
EP3466398A1 (de) 2017-10-05 2019-04-10 Rhodia Operations N-hydrocarbyldiamid-zusammensetzung mit gelierenden eigenschaften
WO2019068914A1 (en) 2017-10-05 2019-04-11 Rhodia Operations FORMULATIONS COMPRISING SURFACTANTS, ORGANIC LIQUIDS AND VISCOSITY IMPROVERS
WO2019068913A1 (en) 2017-10-05 2019-04-11 Rhodia Operations FORMULATIONS COMPRISING BIOLOGICALLY ACTIVE PRINCIPLES

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3632783A (en) * 1969-05-27 1972-01-04 Hall Co C P Treatment of mosquito bites employing certain tetraalkyl diamides
JPS57154102A (en) * 1981-03-19 1982-09-22 Takako Mori Insecticidal method
ATE14364T1 (de) * 1981-11-07 1985-08-15 Siegfried Ag Verfahren zur bekaempfung eines breiten spektrums von unkraeutern in kulturen und zusammensetzung fuer dieses verfahren.
EP0143303A3 (de) 1983-10-29 1986-04-30 Bayer Ag Verfahren zur Herstellung von substituierten Bernsteinsäureamiden
CA1294981C (en) 1984-11-29 1992-01-28 Robert A. Dubbert 1,6 hexanediamides from 3-pentenamides
DE4404222A1 (de) * 1994-02-10 1995-08-17 Bayer Ag Verwendung von Dicarbonsäure-bis-dimethylamiden als Kristallisationsinhibitoren
UA52701C2 (uk) * 1996-10-11 2003-01-15 Басф Акцієнгезельшафт Твердий засіб захисту рослин та спосіб його одержання, спосіб боротьби з небажаним ростом рослин, спосіб боротьби з шкідливими грибами і тваринами-шкідниками та спосіб регулювання росту рослин
US6391451B1 (en) * 1999-09-07 2002-05-21 Basf Aktiengesellschaft Surface-treated superabsorbent polymer particles
FR2872824B1 (fr) * 2004-07-06 2006-09-22 Rhodia Chimie Sa Procede pour epaissir un milieu liquide concentre en agents tensioactifs
FR2910000B1 (fr) * 2006-12-19 2009-10-16 Rhodia Recherches & Tech Nouveaux composes bis(dialkylamides), procede de preparation et utilisations.

Also Published As

Publication number Publication date
AR075276A1 (es) 2011-03-23
FR2936129A1 (fr) 2010-03-26
FR2936129B1 (fr) 2012-10-12
EP2328862A1 (de) 2011-06-08
WO2010031867A1 (fr) 2010-03-25
US20120029092A1 (en) 2012-02-02
ES2557597T3 (es) 2016-01-27

Similar Documents

Publication Publication Date Title
EP2252144B1 (de) Verwendung von esteramiden als lösungsmittel, esteramide als solche, sowie verfahren zur herstellung von esteramiden
EP2102148B1 (de) Neue bis(dialkylamid)verbindungen, verfahren zu ihrer herstellung und anwendungen davon
EP2280936B1 (de) Verbindungen vom etheramidtyp, herstellungsverfahren und anwendungen
EP2328862B1 (de) Diamide enthaltendes produkt, verfahren zu dessen herstellung und anwendungen davon
EP2547199B1 (de) Neuartige verwendung von esteramidverbindungen
EP2547651B1 (de) Esteramidverbindungen, verfahren zu ihrer herstellung und verwendung
WO2014132178A2 (fr) Derives du furfural a titre de vehicule
EP2491008B1 (de) Ether-amid-verbindungen und ihre verwendung
FR2926699A1 (fr) Utilisation d'esteramides, nouveaux esteramides et procede de preparation d'esteramides

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110317

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20120302

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150511

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 756497

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009034374

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2557597

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160127

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 756497

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160221

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160121

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160222

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160122

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009034374

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

26N No opposition filed

Effective date: 20160722

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160921

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160921

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160921

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160922

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20090921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151021

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181120

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20190912

Year of fee payment: 11

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20201001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201001

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230624

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230803

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230808

Year of fee payment: 15

Ref country code: DE

Payment date: 20230802

Year of fee payment: 15

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20240222 AND 20240228

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602009034374

Country of ref document: DE

Owner name: SPECIALTY OPERATIONS FRANCE, FR

Free format text: FORMER OWNER: RHODIA OPERATIONS, AUBERVILLIERS, FR